Azo-disulfide triazine dyestuffs



United States Patent 3,261,825 AZO-DISULFIDE TRIAZINE DYESTUFFS Thomas E. Lesslie, Mount Holly, and Gordon A. Geselbracht, Charlotte, N.C., assignors to Martin-Marietta Corporation, a corporation of Maryland No Drawing. Filed Mar. 11, 1963, Ser. No. 264,046 14 Claims. (Cl. 260-153) The present invention relates to dyestuffs, and more particularly to improved a o-disulfide dyestuffs and to the method for making same.

The azo-disulfide dyestuffs of the present invention are particularly characterized in that they have the formula wherein R is a substituted or unsubstituted aryl substituent, R is a substituent selected from the group consisting of halogen, amine, and substituted amine, and R is a chromophoric group. For example, the compounds of the present invention may have the formula r -r r N N N C O wherein D is the radical of a member selected from the group consisting of diaminodiphenyldisulfides and diaminodinaphtyldiswlfides, D being linked to the triazines via its amino groups; R, is a member selected from. the group consisting of chlorine and phenylamino; Z is the nadical of a member selected from the group consisting of acetoacet-ortho-anisidide, 3-methyl-5-pynazolone, 1- phenyl-3 methyl-5-pynazolone, 2,4-dihydroxyquinoline, ,8- naphthol, and 3-hyd1 oxy-2-naphth-ortho-anisidide; and in which the azo groups are positioned meta or para with respect to the amino groups attached to the phenyl rings.

Generally speaking, the novel vazo-disulfidle dyestuffs of the present invention are synthesized by condensing one molecular proportion of a chromophore with one molecular proportion of a cyanuric trihalide, and condensing one molecular proportion of the resulting product with onehalf molecular proportion of a diamino disulfide having the formula H NRSS-RNH wherein R is a substituted or unsubstituted aryl substituent, to produce the dyestuff. Optionally, the dyestuff may be further reacted by condensing one molecular proportion thereof with two molecular proportions of an amine or substituted amine, e.g. by replacing the final halogen of each cy'anu'ric nucleus.

One of the objects of the present invention is to produce azo-disulfide dyestuffs that have good wash fastness when applied to cotton or regenerated cellulose.

Another object of the present invention is to produce azo-disulfide dyestuffs that provide very high color yield when applied by the reduction-oxidation dyeing method.

Another object of the present invention is to produce azo-disulfide dyestuffs that have good light fiastness.

Another object of the present invention is to produce azo-disulfide dyes that show little if any, change of shade or light fastness when fabrics dyed therewith are aftertreated with resin.

Another object of the present invention is to produce a valuable new group of azo-disulfide dyestuffs having therein member-s covering a wide color range.

Certain azo-disulfide dyestuffs have been known for a number of years, but the azo-disulfide dyestuffs have been never gone into commercial production.

The azo-disulfide dyestuffs of the prior art are all subject to disadvantages and limitations, among which are the following.

Textile fibers may be dyed with azo-disulfide dyestuifs by a reduction-oxidation method comprising the steps of applying a dye composition comprising azo-disulfide dyestuff and reducing agent to the fibers, steaming the fibers, optionally washing the fibers, and oxidizing the dyestuff, preferably with an acid-oxidizing agent, which method is claimed in US. patent application Serial No. 264,413, filed on even date herewith. Although the washing step is preferred, to prevent dilution of the oxidizing bath with excess reducing agent and to avoid formation of hydrogen sulfide gas when the oxidizing bath is acid, many of the known azo-disulfide dyestuffs are removed in substantial quantity from the fibers by washing prior to oxidizing.

Some of the known azo-disulfide dyestuffs "have poor light fastness properties.

The above disadvantages and limitations have been overcome by the aZo-disulfide dyestuffs of the present invention, as follows.

It has been found that the azo-disulfide dyestuffs of the present invention may be used to dye cotton and regenerated cellulose textile fibers by the reduction-oxidation method and may be washed following reduction and prior to oxidation without noticeable removal of dye; that the resulting dyeings have good wash fastness and light fastness, and may be after-treated with resin without changing the shade or light fastness property of the dyeing. Moreover, a wide range of colors may be obtained by using different chromophores in synthesizing the dyestuffs.

The substituted or unsubstituted aryl substituent of the dyestuff, represented by R, will usually be phenyl, substituted phenyl, naphthyl, or substituted naphthyl, and preferably phenyl for reasons of economy; and selection of the aryl or substituted aryl substituent has no apparent effect on the azo-disulfide dyestuff or its dyeing properties.

The R, substituent will be selected from the group consisting of halogen, amine, and substituted amine. For reasons of economy, the R substituent will preferably be Cl, as selection of a halogen for the R substituent omits the necessity for an additional condensation reaction to replace the halogen, and cyanuric trichllori'de is a more economical starting material than the other cyanuric tri'halides. The R substituent may be varied widely without changing the properties of the dyestuff.

The R substituent of the dyestuff is a chromophoric group, and its selection determines the color of the dyestuff. The chromophoric group of the dyestufi may be attached to the cyanuric trihalide through an NH, S, or O linkage, and therefore the chromophore which is selected fior condensation with the cyanuric trihalide should contain a condensable group, such as a free amino group, a free thiophenol group, or a free hydroxy group.

Ohromophores are well understood in the dye synthesis art. Witt, in 1876, pointed out that all colored organic molecules contain one or more doubly bonded groups such as -N=N-, C=C C=N-, C=O', and N O which he called chromophores. As stated by Dr. Lubs, In more recent usage, the termfchromophore) is often applied to a complete conjugated unit, a group of atoms bearing a continuous chain or network of interacting mobile electrons which may be excited by a single photon, and this more modern usage is the definition herein intended.

The novel azo-disulfide dyestuffs of the present invention are synthesized by a series of condensation reactions, whereby one molecular proportion of a condensable chromophore is )condensed with one molecular proportion of a cyanuric trihalide (trihalogeno triazine) to form a dihalogeno-triazine chromophoric intermediate; and one molecular proportion of the dihalogeno-triazine-chromophoric intermediate is condensed With one-half molecular proportion of a diamino disulfide having the formula H NRSS--R-NH wherein R is an aryl or substituted aryl group, to form an azo-disulfide dyestutf having two mono-halogeno-triazine-chromophoric groups coupled to the diamino disulfide through imino linkages; and optionally conducting a third condensation reaction to displace the remaining halogens with amines or substituted amines, as by condensing one molecular proportion of the halogen containing azo-disulfide dye with two molecular proportions of an amino, aromatic amino or aliphatic amino or compound.

The chromophores may be prepared in any convenient manner, such as 'by diazotising a nitroarylamine, coupling one mole of the diazotized nitroarylamine to one mole of 3amethyl-S-pyrazolone, reducing the resulting product with sodium sulfhydrate, filtering and drying.

In condensing the chromophore with the trihalogeno triazine, one mole of each is dissolved in organic solvent and alkali is added to reduce the acidity. The condensation is conducted at about 5 C. The resulting dihalogeno-triazine-chromophoric intermediate has the formula wherein X is a halogen and R is a chromophoric group.

In condensing the above dih-alogeno-triazine-ohromophoric intermediate with the diamino disulfide, one mole of the dihalogenotriazine-chrornophoric intermediate and one-half mole of the diamino disulfide are dissolved in organic solvent, lallcali is added to reduce the acidity, and the condensation reaction is conducted at about 15- 20 C. The resulting azo-disulfide dyestutf has the formula wherein X is a halogen, R is an aryl or substituted aryl substituent, and R is a c'hromophoric group. This 2120- disulfide dyestufi may be recovered, as by distilling off the organic solvent, adding water to the dye residue, filtering, washing the dye with warm Water until the runolf is clear, and drying the dyestufi.

The third, and entirely optional, condensation reaction may be conducted without isolating the above azo-disulfide dyestuif, and comprises condensing one mole of the above azo-disulfide dyestuif, which contains two monohallogeno triazine rings, with two moles of an amino, aromatic amino or aliphatic amino compound to split out the last remaining firom each triazine ring and connect the amino type compounds to the triazine rings by means of nitrogen atom linkage. This final condensation reaction is conducted at 3060 C., with the reactants in organic solvent, and with alkali added to the solution to reduce the acidity. The resulting azo-disulfide dyestuii may be recovered as described above.

Organic solvents such as acetone and dioxane, and a-lkalis such as sodium carbonate and sodium hydroxide are suitable for use in the above condensation reactions, and the condensation reactions are conducted at pH of about 5.0-6.5.

Several illustrative and non-limiting examples of making the dyestuffs according to the present invention follow.

Example I The ohromophore is prepared by diazotising one mole of pa-ra-nitroaniline and coupling it to one mole of acetoacetortho-anisidide. This may be done by adding 138.06 gins. paranitroaniline to one liter of water at 20 C., and adding thereto 250 gms. of concentrated hydrochloric acid at room temperature with stirring until dissolved. The resulting solution is cooled to 0 C. and held at that temperature while a slight excess of NaNO;;, as shown on KI paper, is added thereto with stirring, about 70 gms. of NaNO will be thus added. In a separate container, add 207 gms. of 100% acetoacet-ortho-anisididle to one liter of water at 50 C., and dissolve therein gms. of a 50% aqueous solution of NaOH at room temperature to form a solution of the sodium salt of acetoacet-ortho-anisidide. Cool the solution to 5 C. and add thereto 200 guts. of sodium acetate buffer, and thereafter add to the buffered solution enough 110% aqueous solution of acetic acid at room temperature to give the solution a pH of 6.5-6.8. While maintaining the solution at 0 C., add slowly thereto with stirring, over a period of 15 minutes, the above prepared solution of diazotized para-nitroaniline and stir the combined solutions at 0 C. until coupling is completed, i.e." for about 60 additional minutes. The coupled product is filtered and washed free of inorganics, and the press cake is reduced with gms. of sodium sulfhydrate, filtered, washed with warm water and dried. The chromophore, 4-aminoazoaminophenylazoacetoacet ortho-anisidide, results as a dry powder.

The chrornop'hore is condensed with a cyanuric trih alide as follows. In a separate container, one mole of 2,4,6- trichloro-1,3,5-triazine (184 gms.) is dissolved in 1,000 gms. of acetone at 25 C., and the solution is cooled externally to 5 C. Gradually, during a period of 2-3 hours, one mole (326 gins.) of the 4-aminoazoaminophenylazo acetoacet-ortho-anisidide powder is added to the acetone solution of cyanuric chloride, while the solution is held at 5 C. Following additon of the 4-aminoazoaminophenylazo acetoaoet-ortho-anisidide, the solution is held for an additonal hour at 5 C., w hereafter 265 gms. of a 20% aqueous solution of soda ash is gradually added to the solution during a period of 30 minutes, while the solution is maintained at 5 C. by external cooling. The solution is stirred at 5 C. until condensation is completed, i.e. about 30 additional minutes. The solution is tested for free amine by dianotising a sample and coupling with beta-naphthol, and the absence of free amine indicates that coupling of the 4-aminoazoaminophenylazoacetoacet-ortho-anisidide to the cyanuric chloride is complete, a dihalogeno-triazine ohromophoric intermediate having been formed.

The dihalogeno-triazine-chrornophoric intermediate is then condensed with a diamino disulfide as follows. Add one-half mole (124 gms.) of 4:4'-di-aminodiphenyldisulfide, which has been dissolved in 300 gms. of acetone, to the above solution, allowing the temperautre to increase to 20 C. Next, add 265 gms. of a 20% aqueous solution of soda ash gradually, during a period of 30 minutes. The solution should now be slightly acid (show neutral on congo paper). Warm the solution to 60 C., distill off the acetone, replace with an equal volume of water, filter to collect the light yellow precipitate, wash the precipitate with warm water until the run-off is clear, and dry the yellow precipitate at about 80 C.

5 6 The light yellow precipitate dyes cotton and rregen- Example 111 erated cellulose bright greenish yellow shades and is an azo-disullfide dyestuff having the following chemical for- Thls eXamP1e 1S as EX amP1e except thatone lt mole of meta-,mtroanllme 1s substituted for the para-n1tro- N f/ I NE NH I l N N I] OCH; ILI OCH: t OHaCC=(|J-NH oH,-( 1-o= ;-NH

0 OH 0 0H Example II aniline and one mole (98 gms.) of 3-methyl-5-pyrazolone is substituted for the acetoacet-ortho-anisidide.

ThlS example is the same as Exarnple I above, exceg The resulting azo-disulfide dyestufi dyes cotton and rethat one mole (138 gms.) of meta-nltroamhne 1s substi- 3Q generated cellulose 21 bright yellow shade, and has the tuted for the para-nitroanlhne. following formula:

The resulting azo-disulfide dyestuif dyes cotton and regenerated cellulose a greenish yellow and has the following chemical formula:

-OCHa 7 8 Example IV Example Vl This example is the same as Example I, except that one This example is the same as Example I above except mole (174 gms.) of 1-phenyl-3-methyl-5-pyra2olbne is that one mole of 1-pheny1-3-methyl-5-pyrazolone is substisubstituted for the aeetoacet-ortho-anisidide. tuted for the acetoacet-ortho-anisidide and one-half mole The resulting azo-disulfide dyestuff dyes cotton and re- 5 (174 gms.) of 4:4'-diaminodinaphthyldisulfide is substigenerated cellulose a bright orange, and has the following tuted. for the 4:4diaminodiphenyldisulfide. chemical formula:

N f NH NH 11 I (HI C=CN=N N= -0=c O l Q N l N =C-CH3 CHaC= Example V 30 The resulting dyestuif dyes cotton and regenerated cel- This example is the same as Example I above except lulose fibers'a bright orange and has the following forthat one mole (138 gms.) of meta-nitroaniline is substimula:

2k ope J-N s-s- N--(|3 s-o1 N N N f NH NH )11 OH N=NC=C N=NO=() HBO-C: HBC-"C=N tuted for the para-nitroaniline and one mole (174 gms.) 55 Example of 1-phenyl-3-methyl-5-pyrazolone is substituted for the This example is the same as Example I above except acetoacet-ortho-anisidide. that one mole of 1-phenyl-3-rnethyl-5-pyrazolone is substi- The resulting dyestuif dyes cotton and regenerated celtuted for the acetoacet-ortho-anisidide and one-half mole lulosi-c fibers a bright yellow shade, and has the following (204 gms.) of 4:4-diamino-3z3'-dimethoxynaphthyldisulchemical formula: 60 fide is substituted for the 4:4'-diaminodiphenyldisulfide.

o1-c \(I}HN@SSNHC c c1 N N N f F NH NH 11 oH C=CN=N N=N-C=C 3,261,825 9 10 The resulting dyestutf dyes cotton and regenerated cel- Example IX lulose a bnght orange and has the followmg formula: This example is the Same as Example I above, except Example VIII This example is the same as Example I except that one mole (161 gms.) of 2,4-dihydroxy-quinoline is substituted for the acetoacet-ortho-anisidide.

The resulting azo-disulfide dyestufi dyes cotton and rethat one mole (144 gms.) of beta-naphthol is substituted for the acetoacet-ortho-anisidide.

The resulting dyestufi may be used to dye cotton and regenerated cellulose fibers a reddish-brown and has the following formula:

NH r m generated cellulose fibers a reddish-orange and has the following formula:

1 1 Example X )K r t /N\ i l g Q? N N r r NH NH Example XI This example is the same as Example I above, except 40 that one-half mole (158.5 gms.) of 2,2'-dichloro-4:4- diaminodiphenyldisulfide is substituted for the 4:4'-diaminodiphenyldisulfide.

The resulting dyestulf dyes cotton and regenerated cellulose fibers a bright greenish-yellow and has the following formula:

Example XII The chromophore is prepared by diazotising one mole phenyl-3-methyl-5-pyrazolone, in a manner analogous to that described in Example I.

One mole of the chromophore is condensed with one mole of 2,4,6-trichloro-1,3,5-triazine in a manner analogous to that described in Example I to produce a dihalogeno-triazine-chromophoric intermediate.

One mole of the dihalogeno-triazine-chromophoric intermediate is condensed with one-half mole of 4:4-diaminodiphenyldisulfide, in a manner analagous to that described in Example I, and the slightly acid acetone solution of the resulting product is preserved.

Two moles (186 gms.) of aniline are added to the slightly acid acetone solution described just above, allowing the temperature to rise to 45 C. Gradually, during a period of 30 minutes, 530 gms. of 20% aqueous solution of soda ash are added. The solution should be slightly acid (show neutral on congo paper) at this point and the condensation reaction be completed. Warm the solution to 60 C. and recover thedyestulf as deof para-nitroaniline and coupling it to one mole of 1- 75 scribed in Example I.

13 14 The resulting dyestuif may be used to dye cotton and which upon being hydrolyzed causes cleavage, yielding regenerated cellulose fibers reddish-orange, and has the a free mercapto group attached to the R substituent, are following formula: the chemical equivalent of those claimed herein, and

H N H H N H i i i l o r lH rim OH OH 1 I=NC=( N=N-c= '3 Q l Q N N CHaC=N CHaC=N The azo-disulfide dyestuffs of the present invention may are intended to be covered by the appended claims, inasbe used to dye and print cotton and regenerated cellulose much as these equivalent dyes form the azo-disulfide dyetextile fibers by the reduction-oxidation method. stuffs of the present invention (the RSS-R form) Dyeings may be made with the azo-disulfide dyestuffs upon being oxidized on the fibers. of the present invention as follows. Pad onto the fabric What is claimed is: an aqueous dispersion of the azo-disulfide dye at 150 1. Acompound of the formula F., 2 oz. of dye per gallon of water, allowing 85% pick- N N up based on fabric weight; dry the fabric; pad aqueous solution of sodium sulphide reducing agent onto the fabric, 10 oz. sodium sulphide per gallon of water at N N N N 150 F.; steam the fabric with neutral air-free steam for one minute at 2l22l5 F.; wash the fabric with I I water at 140 F.; pad aqueous solution of oxidizing agent I T onto the fabric, 1 oz. glacial acid and 1 oz. sodium bichromate per gallon of water at 140 F.; rinse in water; scour; and dry.

Cotton or regenerated cellulose may be printed with the azo-disulfide dyestuffs of the present invention by applying to the fabric a printing pa e con i ing f 10 40 wherein D is the radical of a member selected from the gms. starch-tragacanth gum, 4 grns. di(sodiocarb0xy group consisting of diaminodiphenyldisulfides and dimethyl) trithiocarbonate reducing agent, 4 gms. diethylaminodinaphtyldisulfides, D being linked to the triazines 6H6 y 4 gms. urea, 3 gms. NaOH, and 15 gmS- of via its amino groups; R is a member selected from the 20% aqueous dispersion of azo-disulfide dyestuif; drying group consisting of chlorine and phenylamino; Z is the the fabric; steaming the fabric for 2-10 minutes with radical of a member selected from the group consisting neutral air-free steam at 212225 F. to reduce the dyeof acetoacet-ortho-anisidide, 3-methyl-5-pyrazolone, 1-

stuff; oxidizing the dyestuif by immersing the fabric for henyl-3-rnethy1-5-pyrazolone, 2,4 dihydroxyquinoline, 15 seconds in an acid-oxidizing bath containing 1.5 oz. fl-naphthol, and 3-hydr0 y-2-naphth-orth0-anisidide; nd

of glacial acetic acid and 1 oz. of sodium bichromate per in whi h the azo groups are positioned meta or para gallon of Water at rinsing in Water; scouring and with respect to the amino groups attached to the phenyl drying the fabric. rings.

It is believed that the chemistry of the dyeing and 2, Acompound fth f l printing reaction is as follows. The azo-disulfide dye- N H H N stuffs of the present invention contain a disulfide linkage 1 (RSSR), which should be considered the normal (6-31 oxidized state of the dyestuff. Upon reduction, the N N N N dye molecule is broken between the sulfur atoms to form two molecules, RSNa+RSNa, in which I 1 reduced form it penetrates the fibers. The oxidizing I I agent then restores the azo-disulfide dyestulf to the RSSR, or normal oxidized state, firmly fixed upon the fibers.

Therefore, it will be understood that dyes having the formula N=NZ N=NZ H N wherein R is a substituent selected from the group conl sisting of phenyl, naphthyl, chlorine substituted phenyl, 1| and methoxy substituted naphthyl; R is a substituent selected from the group consisting of chlorine and phenyl- 0 amino; Z is the radical of a member selected from the group consisting of acetoacet-ortho-anisidide, 3-methyl- 5 pyrazolone, 1 phenyl-3-methyl-5-pyrazolone, 2,4-diwherein R is an aryl or substituted aryl substituent, R hydroxyquinoline, B-naphthol, and 3-hydroxy-2-naphthis a member selected from the group consisting of haloortho-anisidide; and in which the azo groups are posigen, amine, and substituted amine, R is a chromophoric tioned meta or para with respect to the amino groups group, and Y is a substituent, such as -CN or NaO S, attached to the phenyl rings.

4. A compound of the formula 5. A compound of the formula 6. A compound of the formula 1 7 7. A compound of the formula 8. A compound of the formula 9. A compound of the formula 10. A compound of the formula 19 11. A compound of the formula 12. A compound of the formula 0 N H 1 w 0 H O "W N i S s m 0 l 0 N H H N H c O G N H N o N A Y-N W m 13. A compound of the formula m C O H N H JH W w H m C m C O] H N H n=U O Q5 CH0 P H C 21 14. A compound of the formula K i N 1 I N /N I IIIIH NH 11 $11 N=N O=C N=NC=C N- N- OHaC=N C s-C=N References Cited by the Examiner UNITED STATES PATENTS 2,399,066 4/1946 Schmid et a1 260-153 CHARLES B. PARKER, Primary Examiner. R. J. FINNEGAN, D. M. PAPUGA, Assistalnt Examiners. 

1. A COMPOUND OF THE FORMULA 